Flame retardant compounds and compositions of matter

ABSTRACT

Novel compounds comprising poly(polyhalonorbornenylalkyl)benzene as exemplified by 1,4-bis(1,3,4,5,6,7,7-heptachloro-5-norbornen2-ylmethyl)-benzene are prepared by reacting an aromatic hydrocarbon containing at least two alkyl substituents with 1,2dichloroethylene and thereafter reacting the resultant product with a polyhalo-substituted cycloalkadiene to form the desired compound. These compounds are useful for imparting flame retardant characteristics when admixed with a polymeric substance.

United States Patent 1 Schmerling FLAME RETARDANT COMPOUNDS ANDCOMPOSITIONS OF MATTER 75] Inventor: Louis Schmerling, Riverside, Ill.

73] Assignee: Universal Oil Products Company, Des Plaines, Ill.

22] Filed: Sept. 13, 1973 21] Appl. No.: 397,197

52] US. Cl 260/649 R; 106/15 FP; 117/1385; 77 117/138/81260/25 FP;260/2.5 AJ; 260/45.7 R; 260/61 1.5; 260/881 R 51] Int. Cl. C07c 25/1858] Field of Search 260/649 56] References Cited UNITED STATES PATENTS2,606,910 8/1952 Herzfeld et a1. 260/649 R X 2,673,172 3/1954 Polen260/649 R X 2,952,711 9/1960 Roberts 260/649 R 2,952,712 9/1960 Robertset al..... 260/649 R X 2,967,842 1/1961 Roberts 260/649 R X 1,043,7957/1962 Roberts et a1 260/649 R X 1 July 1,1975

3,090,817 5/1963 Schmerling 260/649 R OTHER PUBLICATIONS Jason et al.,J. Org. Chem, 26, 937-938, 1961. Mamedaliev et al., Chem. Abs., 59,1502f, 1963. Akad. Nauk Azerb, SSR 18, N0. 9, 15-17, 1962.

Primary Examiner-Howard T. Mars Attorney, Agent, or FirmJames R.Hoatson, Jr.; Raymond H. Nelson; William H. Page [57] ABSTRACT Novelcompounds comprising poly(polyhalonorbornenylalkyl)benzene asexemplified by 1,4- bis( 1 ,3,4,5,6,7,7-heptachloro-5-n0rbornen-2-ylmethyl)-benzene are prepared by reacting an aromatic hydrocarboncontaining at least two alkyl substituents with 1,2-dichloroethylene andthereafter reacting the resultant product with a polyhalosubstitutedcycloalkadiene to form the desired compound. These compounds are usefulfor imparting flame retardant characteristics when admixed with apolymeric substance.

8 Claims, No Drawings FLAME RETARDANT COMPOUNDS AND COMPOSITIONS OFMATTER This invention relates to novel compounds comprising apoly(polyhalonorbornenylalkyl)benzene and particularly to the usethereof with polymeric substances to form novel compositions of matterwhich posses the desirable physical characteristics of being resistantto flame or fire retardant.

The novel compounds of the present invention comprising poly(polyhalonorbornenylalkyl )benzenes which are prepared according to themethod hereinafter set forth in greater detail will be useful asadditives to plastics, polymers, copolymers, terpolymers, resins,elastomers, rubbers, textiles and fibers, both naturally occurring andsynthetic in nature, such as cotton, wool, Dacron, nylon rayon, etc.,coatings, paints, varnishes, leather, foams, cellulose acetate butyrate,ethyl cellulose, cellulose propionate, etc., polyolefins such aspolyethylene and polyethylene copolymers, polypropylene andpolypropylene copolymers, polystyrene, polystyrene copolymers,polyvinylacetate or alcohol and copolymers, polyesters, polyurethane,polyphenyl ethers, polycarbonates, polyamides, polyoxymethylenes,polyalkylene oxides such as polyethylene oxide, polyacrylates andcopolymers, polymethacrylates and copolymers with styrene, butadiene,acrylonitrile, etc., epoxy resins, acrylonitrile-butadiene-styreneformulations (commonly known as ABS), polybutylene and acrylic estermodified styrene-acrylonitrile (ASA),methyl-methacrylate-styrene-butadiene terpolymers, etc. whereby thedesirable physical characteristics of flameproofing or fire retardancywill be imparted to the aforementioned materials. This property willpossess special advantages when preparing plastic or resinous materialwhich will be utilized in places which may be subjected to excessiveheat or possible flame such as architectural panels for constructionwork, skydomes, skylights, wall plugs for electrical connections,ashtrays, etc. In addition, the compound when used as a constituent ofpaint, lacquer, varnishes, or protective coatings, films, etc. will alsoimpart a fire resistancy to these compounds and, therefore, render themcommercially attractive as articles of commerce. Furthermore, the flameretardancy of foams such as the polyurethane foams will greatly enhancetheir use as insulating material or soundproofing material. Also,besides imparting the desirable physical characteristics of flameretardancy to the various articles of manufacture, the additives willrender clear plastics or resins more stable to color changes andtherefore will be an important component of these compounds whenever itis desirable that discoloration of the finished product is to be avoidedor will tend to render such articles unusable. It is also contemplatedthat the novel compositions of matter of this invention may also be usedas an insecticide or as an ingredient in insecticidal formulations.

It is therefore an object of this invention to provide novel compoundswhich possess desirable physical characteristics.

Another object of this invention is to provide novel compositions ofmatter comprising a mixture of a polymeric substance and the novelcompound of this invention whereby the finished product will possess thedesirable physical characteristics of flameproofing and fire retardancy.

in one aspect an embodiment of this invention resides in a compoundcomprising a poly( polyhalonorbornenylalkyl )benzene.

Another embodiment of this invention is found in a flame retardantcomposition of matter comprising a polymer and apoly(polyhalonorbornenylalkyl)benzene.

A specific embodiment of this invention resides in a novel compoundcomprising l,4-bis( l ,3,4,5,6,7,7- heptachloro-S-norbornen-2-ylmethyl)benzene.

Another specific embodiment of this invention is found in a flameretardant composition comprising a mixture of polypropylene andl,3,5tris( l,3,4,5,6,7,7- heptachloro-S-norbornen-2-ylmethyl )benzene.

Other objects and embodiments will be found in the following furtherdetailed description of the present invention.

As hereinbefore set forth the present invention is concerned with novelcompounds comprising poly(pol yhalonorbornenylalkyl)benzenes and to theuse thereof as a flame retardant additive to polymeric substances. Thenovel compounds are prepared by the free radicalinduced reaction of apolyalkyl-substituted benzene with l,2-dichloroethylene followed bycondensation of the bisor more highly chloro-allylated reaction productwith a polyhalo-substituted alkadiene, and particularly apolyhalo-substituted cyclopentadiene. Aromatic compounds which may beutilized as starting materials in the present process have attached tonuclear carbon atoms a carbon atom of a saturated hydrocarbon group towhich last named carbon atom is attached at least one hydrogen atom.Thus, the aromatic hydrocarbon has alpha-carbon atoms attached to thearomatic nucleus to which alpha-carbon atom are attached at least onehydrogen atom, thus giving a structural unit which may be represented asfollows:

in which R represents hydrogen or an alkyl group containing from 1 toabout 4 carbon atoms, at least two Rs being alkyl. It is contemplatedwithin the scope of this invention that the alkyl groups may be straightchained or branched chained in configuration. Some specific examples ofthese aromatic hydrocarbons which may be utilized as one of the startingmaterials of the present process will include ortho-xylene, meta-xylene,para-xylene, l,2,3-trimethylbenzene (hemimellitene),l,2,4-trimethylbenzene (pseudocumene), 1,3 ,5- trimethylbenzene(mesitylene), l,2,3,4-tetramethylbenzene (prehnitol 1,2,3,S-tetramethylbenzene (isodurene), l,2,4,5-tetramethylbenzene (durene),pentamethylbenzene, hexamethyl benzene, l ,2- diethylbenzene,1,3-diethylbenzene, 1 ,4- diethylbenzene, l,2,3-triethylbenzene, 1,3 ,5-triethylbenzene, l,2,4-triethylbenzene, l,2,3,4-tetraethylbenzene,l,2,3,S-tetraethylbenzene, l,2,4,5-tetraethylbenzene, pentaethylbenzene,hexaethylbenzene, l,2-di-n-propylbenzene, l,3-di-n-propylbenzene, 1,4-di-n-propylbenzene, 1,2,3-tri-n-propylbenzene,

l,3,S-tri-n-propylbenzene, l,2,4-tri-n-propylbenzene,l,2,3,4-tetra-n-propylbenzene. l,2,3.5-tetra-npropylbenzene, l.2,4,5tetra-n-propylbenzene, penta-n-propylbenzene, hexa-n-propylbenzene,1,2-diisopropylbenzene, 1,3-diisopropylbenzene 1,4-diisopropylbenzene,1,2,3-triisopropylbenzene, l,3,5-triisopropylbenzene,l,2,4-triisopropylbenzene, l,2,3,4-tetraisopropylbenzene,l,2,3,5-tetraisopropylbenzene, l,2,4,5-tetraisopropylbenzene,pentaisopropylbenzene, hexaisopropylbenzene, l ,2-di-nbutylbenzene,1,3-di-n-butylbenzene, 1,4-di-n- V butylbenzene,l,2,3-tri-n-butylbenzene, 1,3,5-tri-nbutylbenzene,l,2,4-tri-n-butylbenzene, l,2,3,4-tetra' n-butylbenzene,l,2,3,5-tetra-n-butylbenzene, l,2,4,5-tetran-butylbenzene,penta-n-butylbenzene, hexa-n-butylbenzene, 1,2-di-sec-butylbenzene,l,3-disec-butylbenzene, l,4-di-sec-butylbenzene,1,2,3-trisec-butylbenzene, 1,3,S-tri-sec-butylbenzene,1,2,4-trisec-butylbenzene, 1,2,3,4-tetra-sec-butylbenzene, 1,2,-3,5-tetra-sec-butylbenzene, 1,2,4,5-tetra-secbutylbenzene,penta-sec-butylbenzene, hexa-secbutylbenzene, l,2-diisobutylbenzene,1,3- diisobutylbenzene, etc. The aforementioned polyalkylsubstitutedbenzenes are reacted with 1,2- dichloroethylene in the presence of afree radical gen erating compound.

The catalysts that may be used in the process of the present inventionare those which are capable of form ing free radicals under the reactionconditions. These include diazonium compounds,metal akyls, and peroxycompounds. Peroxy compounds contain thebivalent radical -0 whichdecomposes to form free r'adi cals which initiate the general reactionof the present invention. Examples of such peroxy compounds are thepersulfates, perborates, percarbonates, of the ammonium and of thealkali metals; peracetic acid, pe rsuccinic acid, dimethyl peroxide,diethyl peroxide, di-tertbutyl peroxide, dipropyl peroxide, acetylbenzoyl peroxide, propionyl peroxide, butyryl peroxide, lauroylperoxide, benzoyl peroxide, tetralin peroxide, urea peroxide,tertiary-butyl perbenzoate, tertiarybutyl hydroperoxide,methylcyclohexyl hydroperoxide, 2,4- dichlorobenzoyl peroxide, methylethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide,

diisopropylbenzene hydroperoxide, paramethane hydroperoxide, isopropylpercarbonate, etc. The Organic peroxy compounds constitute a preferredclass of catalysts for use in this invention. Mixtures of peroxycompound catalysts may be employed or the peroxy compound catalysts maybe utilized in admixture with various diluents as catalysts for theprocess of this invention. Thus organic peroxy compounds which arecompounded commercially with various diluents for use as free radicalgenerating catalysts may be used and include benzoyl peroxide compoundedwith calcium sulfate, benzoyl peroxide compounded with camphor, benzoylperoxide compounded with hydrogenated terphenyls, benzoyl peroxidecompounded with stearic acid, benzoyl peroxide compounded with tricresylphosphate, benzoyl peroxide compounded with dibutyl' ations must betaken into account, First, sufficient energy by means of heat must be tothe reaction system so that the reactants, namely, the selectedpolyalkyl-substituted aromatic hydrocarbon and the polychloroolefin willbe activated sufficiently for condensation to take place when freeradicals are generated by the catalyst. Second, free radical generatingcatalysts such as peroxy compounds, particularly organic peroxides,decompose at a measurable rate with time in a logarithmic functiondependent upon temperature. This rate of decomposition can be andordinarily is expressed as the half life of a peroxide at a particulartemperature. For example, the half life in hours for'ditert-butylperoxide is 17.5 hours at C., 5.3 hours at -l35 C., and 1.7 hours at C.:(calculated. from data for the first 33% decomposition). A'reactionsystem temperature must then be selected so that the free radicalgenerating catalyst decomposes smoothly with the generation of freeradicals at a half life which is not too long. In other words,sufficient free radicals must be present to induce the present chainreaction to take place, and these radicals must be formed at atemperature at which the reactants are in a suitably activated state forcondensation. When the half life of the free radical generating catalystis greater than 10 hours, radicals are notgenerated at a sufficient rateto cause the reaction of the process of th epresent invention to goforward at a detectable rate. Thus the reaction temperature maybe withinthe range of from about 50 to about 300 C. and at least as high as thedecomposition temperature of the catalyst, by whic'h is meant a'tempe'rature such that the half life of the free radical generatingcatalyst is not greater than 10 hours. Since the half life for each freeradical generating catalyst is different at different temperatures, theexact temperature one familiar with the art to select the particulartemperature needed for any particular catalyst. Generally the operatingtemperature does not exceed the temperature at which the half life isnot more than 10 hours by more than about C. since free radicalgenerating catalysts decompose rapidly under such conditions.

However, in some instances temperatures as high as 300 C. may beutilized. The half-life of tert-butyl perb enzoate is less than 10 hoursat about l 10 C., and accordingly when this peroxy compound is used asthe catalyst for this process, the operating temperature is from about 110 C. to about 300 C., but generally not greater than about 265 C. Anoperating temperature of from about 130 C. to about 300 C. is used witha di-tert-butyl peroxide, and from about 75 to about 300 C., butgenerally not greater than about 225 C., with benzoyl peroxide. Littleadvantage is gained if the temperature is too high even though thereactants tend to become more activated in the presence of the freeradical generating catalyst decomposing at a high rate sincedecomposition of the dichloroethylene takes place at temperatures aboveabout 300C.

Although pressure of up to 100 atmospheres may be utilized, the reactionpreferably takes place in liquid phase and thus the pressure willpreferably range 'from i about atmospheric to about 100 atmospheres suchthat a substantial proportion of the reactants is in the liquid phase.Pressure is not an important variable in the process of this invention.However, because of the low boiling points of some of the reactants, itis necessary to utilize pressure withstanding equipment to insure liquidphase conditions. In batch type operations, it is often desirable toutilize pressure withstanding equipment to charge the reactants andcatalyst to the vessel, and to pressure the vessel with or or 50 or moreatmospheres of an inert gas such as nitrogen. This helps to insure thepresence of liquid phase conditions. However, when the mole quantity ofreactants is sufficient, the pressure which they themselves generate atthe temperature utilized is sufficient to maintain the desired phaseconditions. Nitrogen is also conveniently utilized when a glass liner isused along with pressure withstanding equipment. Since the nitrogen ispressured into the vessel prior to heating, it tends to maintain thereactants within the glass liner and thus aids in their removal afterthe passage of the desired period of time at the reaction temperatureselected.

The concentration of the catalyst employed in this process may vary overa rather wide range but for reasons of economy, it is desirable to uselow concentrations of catalyst, such as from about 0.1% to about 10% ofthe total weight of the polychloroolefin and polyalkyl-substitutedaromatic hydrocarbon charged to the process. The reaction time may bewithin the range of less than one minute to several hours, dependingupon temperature and half life of the free radical generating catalyst,as set forth hereinabove. Generally, contact times of at least 10minutes are preferred.

The reaction between the polyalkyl-substituted aro matic hydrocarbon andthe polychloroolefin may be effected in either a batch or continuoustype operation. When utilizing a batch type operation, a quantity of thepolyalkyl-substituted aromatic hydrocarbon and the free radicalgenerating catalyst are placed in an appropriate apparatus which may beprovided with heating and mixing means, adding the polychloroolefin tothe reaction mixture and thereafter heating to a predetermined reactiontemperature while thoroughly admixing the contents of the reactor. Uponcompletion of the desired residence time which may range from about 0.5up to about 10 hours or more in duration, the reactor and contentsthereof are allowed to cool to room temperature and the desiredcondensation product is recovered by conventional means well known inthe art. Another method of effecting the reaction is in a continuoustype of operation. When this method of operation is employed, thepolyalkyl-substituted aromatic hydrocarbon, the polychloroolefin and thefree radical generating compound are continuously charged to a reactorwhich is maintained at the proper operating conditions of temperatureand pressure. Upon completion of the reaction time, the condensationproducts are separated from the reactor effluent which has beencontinuously withdrawn and the unreacted starting materials are thenrecycled to the reaction zone.

The poly(chloroallyl)benzenes which have been produced according to theabovee paragraph are then subjected to a condensation reaction utilizinga polyhalosubstituted cycloalkadiene as the second reactant. Examples ofpolyhalo-substituted cycloalkadienes which may be utilized will include1,2- dichlorocyclopentadiene, l,2,3-trichlorocyclopentadiene,l,2,3,4-tetrachlorocyclopentadiene, l,2,3,4,5-

pentachlorocyclopentadiene, hexachlorocyclopentadiene,l,2-dibromocyclopentadiene, 1.2,3-tribromocyclopentadiene.l,2,3,4-tetrabromocyclopentadiene, l,-2,3,4,5-pentabromocyclopentadiene, hexabromocyclopentadiene, etc. It isalso contemplated within the scope of this invention thatpolyhalo-substituted conjugated cyclohexadienes may also be employed,although not necessarily with equivalent results. Representativeexamples of these cyclohexadienes of the 1.3- cyclohexadiene type,hereinafter referred to as cyclohexadienes, will include 1,2-dichlorocyclohexadiene, l,2,3-trichlorocyclohexadiene,1,2,3,4-tetrachlorocyclohexadiene, 1,2,3 ,4,5-

pcntachlorocyclohexadiene, l,2,3,4,5,5-hexachlorocyclohexadienel,2,3,4,5 ,5,6,6-octachlorocyclohexadiene, the correspondingbromo-substituted compounds, 7 The condensation between thepolyhalosubstituted cycloalkadiene and the poly(chloroallyl)- benzene;may be effected at elevated temperatures ranging from about to about 200C. or more and preferably at atmospheric pressure. It is alsocontemplated within the scope of this invention that superatmosphericpressures may also be employed in this step of the reaction, anysuperatmospheric pressure being afforded by the introduction of asubstantially inert gas such as nitrogen into the reaction zone, theamount of pressure which is to be employed being that which issufficient to maintain a major portion of the reactants in a liquidphase. In addition, if so desired, an inert organic solvent may also beemployed in this step of this reaction, said solvents including paraffmssuch as npentane,,n-hexane, n-heptane, cyclopentane, cyclohexan e,methylcyclopentane, etc,

As in the first step of the reaction, the condensation of the tworeactants may also be effected in either a batch or continuous typeoperation. For example, when a batch type operation is used, a quantityof the poly(- chloroallyl,)benzene and the polyhalo-substitutedcycloalkadiene (and, if desired, a diluent such as toluene) is placed inan appropriate apparatus along with any solvent, if so desired, thereaction apparatus is then heated to the desired operating temperatureand maintained thereat for a predetermined residence time which againmay range from about 0.5 up to about 10 hours or more in duration, thereactants being thoroughly admixed during the reaction period. In theevent that superatmospheric pressures are to be employed, the reactionapparatus will comprise an autoclave of the rotating or mixing type, thereactants being charged to the autoclave which is thereafter sealed,raised to the required operating pressure by means of introduction ofthe inert gas and thereafter heated to the desired operatingtemperature. Upon completion of the desired residence time, heating isdiscontinued, the autoclave is allowed to return to room temperature,the excess pressure is vented and the reaction mixture is recoveredtherefrom. The desired reaction product is then recovered byconventional means such as washing, drying, fractional distillationunder reduced pressure followed by treatment of the bottoms byrecrystallization in order to recover the desired product.

Examples of novel compounds of the present invention which may beprepared by the methods hereinbefore set forth will include thosecompounds characterized by the formula;

in which X is selected from the group consisting of hydrogen and halogenatoms, especially chlorine and bromine, at least two Xs being halogen, Ris selected from the group consisting of hydrogen and lower alkylgroups, R is selected from the group consisting of hydrogen and loweralkyl radicals containing from 1 to about 4 carbon atoms and n is aninteger of from 2 to 6.

Some representative examples of these compounds will include1,4-bis(1,3,4-trichloro-5-norbornen-2- ylmethyl )benzene, l,4-bis-(l,3,4,5,6-pentachloro-5- norbornen-Z-ylmethyl )benzene, l,4-bis(l,3,4,5,6,7,7- heptachloro-S -norbornen-2-ylmethyl )benzene, 1,3- bis( 1,3,4-trichloro-S-norbornen-Z-ylmethyl )benzene, 1,3-bis( l,3,4,5,6-pentachloro-5-norbornen-2- ylmethyl)-5-methylbenzene, l,3-bis(l,3,4,5,6,7,7- heptachloro-S -norbornen-2-ylmethyl )benzene, 1,2- bis( 1,3,4-trichloro-5-norbornen-2-ylmethyl )benzene, l,2-bis( l,3,4,5,6-pentachloro-5-norbornen-2- ylmethyl)benzene, l,2-bis(l,3,4,5,6,7,7-heptachloro- 5-n0rbornen-2-ylmethyl)benzene, l,3,5-tris( l,3,4- trichloro-5-norbornen-2-ylmethyl )benzene, 1,3,5- tris( 1 ,3,4,5,6-pentachloro-5-norbornen-2- ylmethyl )benzene, 1,3,5-tris( 1,3,4,5,6,7,7- heptachloro-S-norbornen2-ylmethyl)benzene, 1,2,3- tris(l,3,4-trichloro-5-norbornen-2-ylmethyl)benzene, l,2,3-tris( l,3,4,5,6-pentachloro-5-norbornen-2- ylmethyl)benzene, l,2,3-tris(l,3,4,5,6,7,7- heptachloro-S-norbrnen-2-ylmethyl)benzene, 1,2,4- tris( l,3,4-trichloro--n0rbornen-2-ylmethyl)benzene, l,2,4-tris(1,3,4,5,6-pentachlor0-5-norbornen-2- ylmethyl)benzene, l,2,4-tris(l,3,4,5,6,7,7- heptachloro-S-norbornen-2-ylmethyl)benzene, 1,2,3,-4-tetra( 1,3 ,4-trichloro-5-norbornen-2- ylmethyl)benzene,l,2,3,4-tetra( l,3,4,5,6- pentachloro-5norbornen-2-ylmethyl)benzene,1,2,3,- 4-tetra( l,3,4,5,6,7,7-heptachloro-5-n0rbornen-2- ylmethyl)benzene, l,4-bis( l,3,4,5,6-pentachloro-5- norbornen-Z-ylmethyl )-2 ,3,5 ,o-tetramethylbenzene, l,4-bis( l,3,4,5,6,7,7-heptachloro-5-norbornen-2- ylmethyl )-2,3 ,5,6-tetramethylbenzene, 1,3- bis( I ,3,4,5,6-pentachloro-5-norbornen-2-ylmethyl 2,4,5,-tetramethylbenzene,l,3-bis( l,3,4,5,6,7,7-heptachloro-S-norbornen-2-ylmethyl)-2,3,5,6-tetramethylbenzene,l,3-bis[a-(1,3,6-trichloro- Snorbornen-Zyl )ethyl Ibenzene, l,2-bis[a-(l,3,4,5 ,6- pentachloro-S-norbornen-2-yl )ethyl]benzene, 1,2- bis[oz-(l,3,4,5,6,7,7-heptachloro-5-norbornen-2- yl)ethyl]benzene, l,3-bis[0z-(1,3,6-trichloro- 5norbornen-2-yl)-ethyl]benzene, 1,3-bis[a-(l,3,4,5,6-pentachloro-5-norbornen-2-yl)ethyl ]benzene, 1,3- bis[a-(l,3,4,5,6,7,7-heptachloro-5-norbornen-2- yl)ethyl]-benzene,l,4-bis[a-(1,3,4-trichloro-5- norbornen-Z-yl )ethyl]benzene, l,4-bis[a-( l,3,4,5 ,6- pentachloro-S-norbornen-2-yl)ethyl]benzene, l ,4-bis[a-(1,3,4,5,6,7,7-heptachloro-5norbornen-2- yl )ethyl ]benzene,l,3,5-tris[o 1,3,4-trichloro-5- norbornen-Z-yl)ethyl]benzene,l,3,5-tris[0z-( l ,3,4,5,6- pentachloro-S-norbornen-2-yl )ethyl]benzene, 1,3 ,5- tris[a-(1,3,4,5,6,7,7-heptachloro-5-norbornen-2- yl)ethyl ]benzene, l,2-bis[a-(1,3,6-trichloro-5-norbornen-2-yl)propyl]benzene, l,2-bis[a-( 1,3,4,5 ,6-pentachloro-S-norbornen-2-yl)propyl] benzene, 1,2- bis[a-(l,3,4,5,6,7,7-heptachloro-5-norbornen-2- yl)propyl lbenzene,l,3-bis[0z-(1,3,4-trichloro-5- norbornen-Z-yl)propylJbenzene,l,3-bis[a-( 1 ,3,4,5 ,6- pentachloro-S -norbornen-2-yl )propyl ]benzene,1,3- bis[a-( l,3,4,5,6,7,7-heptachloro-5-norbornen-2- yl)propyl]benzene, l,4-bis[a-( 1,3,6-trichlor0-5- norbornen-Z-yl)propyl]-benzene,l,4-bis[a-(1,3,4,5,6- pentachloro-S-norbornen-2-yl)propyl]benzene, l ,4-bis[a-( l ,3,4,5,6,7,7-heptachloro-5-norbornen-2- yl)propyl]benzene,l,3,5-tris[oz-(1,3,6-trichloro-5- norbornen-Z-yl )propyl]benzene, l,3,5-tris[al ,3,4,5,6-pentachloro-5-norbornen-2- yl )propyl]benzene,l,3,5-tris[a-(1,3,4,5,6,7,7' heptachloro-S-norbornen-2yl)propyl]benzene,l ,2- bis( 3-chloro-l ,4-dibromo-5-norbornen-2- ylmethyl)benzene,l,2-bis(3-chloro- 1 ,4,5,6- tetrabromo-S-norbornen-2-ylmethyl)benzene, l,2- bis( 3-chlorol ,4,5 ,6,7,7-hexabromo-5-norbornen-2- ylmethyl)benzene, 1,4-bis-(3chloro-l,4-dibromo-5- norbornen-Z-ylmethyl )benzene,l,4-bis( 3-chlorol,4,5,6-tetrabromo-5-norbornen-2-ylmethyl )benzene,l,4-bis( 3-chloro-l ,4,5,6,7,7-hexabromo-5-norbornen- 2-ylmethyl)benzene, l,3,5-tris( 3-chlorol ,6-dibrom o-5-norbornen-2-ylmethyl)benzene,l,3,5-tris(3-chlorol,4,5,6-tetrabromo-5-norbornen-2-ylmethyl)benzene,1,3 ,5-tris( 3-chloro- 1 ,4,5 ,6,7,7-hexabromo-5-norbornen-2-ylmethyl)benzene, l,4-bis[a-(3-chloro-1,4-dibromo-5-norbornen-2-yl )ethyl]benzene, 1 ,4- bis[a-( 3-chlorol,4,5,6tetrabromo-5-norbornen-2- yl )ethyl ]benzene, 1 ,4-bis[a-(1chlorol ,4,5,6,7,7- hexabromo-S-norb0rnen-2-yl)ethyl]benzene, etc. Itis to be understood that the aforementionedpoly(polyhalonorbornenylalkyl)benzenes are only representative of theclass of compounds which may be prepared and that the present inventionis not necessarily limited thereto.

The aforementioned poly(polyhalonorbornenylalkyl)benzenes are admixedwith polymeric compounds of the type hereinbefore set forth in greaterdetail, said polymeric compounds including, but not limited to,polymers, copolymers, terpolymers, resins, polycondensates, rubbers,textiles and fibers, etc., to form novel compositions of matter whichwill possess the desirable physical characteristics of being fireresistant or flame retardant. The novel compounds of the presentinvention are present in an amount ranging from about 1% to about 50% byweight of the final flame retardant composition of matter. It iscontemplated that the desired compositions of matter may be prepared inany suitable manner and the novel compounds may be admixed with thepolymeric substance in a mixer, may be milled, or may be extruded afteradmixing by any means well known in the art, the only criterion beingthat the two components of the mixture be admixed so that there is auniform distribution of the novel compound throughout the entirecomposition of matter, thereby imparting a uniform degree of flameretardancy to the final composition of matter.

Some representative examples of the final novel flame retardantcompositions of matter of the present isoprene and l,3-bis(l,3,4,5,6-pentachloro-- norbornen-Z-ylmethyl)benzene, polyisoprene and1.4 bis( 1 ,3,4,5,-pentachloro-5-norbornen-2 -ylmethyl)- benzene,polyisoprene and l,2-bis-(1,3,4,5,6,7.7-heptachloro-5-norbornen-2-ylmethyl)benzene, polyisoprene and 1,3-bis( l,3,4,5,6,7,7-heptachloro-5- norbornen-2-ylmethyl)benzene, polyisopreneand 1,4- bis(1,3,4,5,6,7,7-heptachloro-5- norbornen-2-ylmethyl)benzene,polyisoprene and 1,3,- 5-tris( l ,3,4,5,6-pentachloro-5-norbornen-2-ylmethyl )benzene, polyisoprene and 1,3 ,5- tris(1,3,4,5,6,7,7-heptachloro-5-norbornen-2- ylmethyl)benzene, polyisopreneand 1,4- bis( 1 ,3,4,5,6,7,7-heptachloro-5-norbornen-2- ylmethyl )-2,3,5 ,6-tetramethylbenzene, polyisoprene andheptachloro-S-norbornen-2-yl)ethyl]benzene, polyisoprene andl,4-bis(3-chloro-1,4,5,6,7,7-hexabromo-5- norbornen-Z-ylmethyl)benzene,polyisoprene and 1,3,-5-tris(3chloro-1,4,5,6,7,7-hexabromo-5-norbornen-2- ylmethyl)benzene,etc. The aforementioned mixture of compounds which also constitute novelcompositions of matter of the present invention will exhibit anunexpectedly high degree of fire resistance when compared to polymericcompounds which do not possess all of the components of the finishedproduct, these aforementioned products being only representative of theclass of compositions of matter of the present invention; and,therefore, this invention is not necessarily limited to thesecompositions of matter.

1,2-bis[a-(l,3,4,5,6,7,7- I

The following examples are given to illustrate the 7 novel compounds andnovel compositions of matter of the present invention, which examples,however, are not intended to limit the generally broad scope of thepresent invention in strict accordance therewith.

EXAMPLE 1 To a rotating autoclave is charged a glass liner containing106 grams (0.1 mole) of para-xylene along with 194 grams (2.0 mole) of1,2-dichloroethylene and 8 grams of di-t-butyl peroxide. The autoclaveis thereafter sealed, the air in the autoclave is swept out withnitrogen and the autoclave is pressured to the initial operatingpressure by the addition of 30 atmospheres of nitrogen. The autoclave isthen heated to a temperature 7 of about 130 C. and maintained thereatfor a period of 4 hours. During this time, the pressure in the autoclavewill rise to about 60 atmospheres. At the end of the 4- hour period,heating is discontinued and the autoclave is allowed to cool to roomtemperature, the excess pressure is discharged and the contents of theauto clave, after neutralization of the hydrogen chloride which isproduced during the reaction, is subjected to fractional distillationunder reduced pressure. The desired product comprisingp-bis(3-chloroallyl)benzene is separated from unreacted startingmaterials and recovered. The dichloroallylbenzene which is preparedaccording to the above paragraph is placed in a reaction flask alongwith hexachlorocyclopentadiene in a mole ratio of 2 moles ofhexachlorocyclopentadiene per mole of bis(chloroallyl)benzene. Inaddition a solvent comprising 1,2,3,4-tetrahydronaphthalene is addedthereto and the reaction mixture is gradually heated from a temperatureof 125 to 175 C. After heating the flask at this temperature for aperiod of 4 hours, the reaction mixture is recovered and subjected tofractional distillation under reduced pressure. The unreacted startingmaterials are distilled over and the'bottoms are recovered. The bottomsare then recrystallized by treatment with xylene and recovered, saidbottoms comprising the desired compound, namely, l,4-bis( l.3,4,5,6,7,7heptachloro-S-norbornen-2-ylmethyl)benzene.

EXAMPLE 11 To a rotating autoclave is charged a" mixture of grams (1.0mole) of 1,3,5-trimethylbenzene (mesitylene), 291 grams (3.0 mole) of1,2-dichloroethy1ene and 8 grams of di-t-butyl peroxide. The autoclaveis sealed and nitrogen pressed in until an initial operating pressure of30 atmospheres is reached. The autoclave is then heated to a temperatureof 130 C. and maintained in a range of from 130-140 C. for a period of 4hours, the pressure during this time reaching about 60 atmospheres. Atthe end of the 4-hour period, heating is discontinued and the autoclaveis allowed to return to room temperature, the pressure dropping back to30 atmospheres. Upon reaching room temperature, the excess pressure isdischarged and the autoclave is opened. The reaction mixture isneutralized to remove the hydrogen chloride which is produced during thereaction, recovered and subjected to fractional distillation underreduced pressure whereby the desired product comprisingl,3,5-tris(3-chloroallyl)benzene is recovered.

To a second rotating autoclave is added 1 mole of thetris(chloroallyl)benzene prepared according to the above paragraph alongwith 3 mole proportions of hexachlorocyclopentadiene and 100 cc. ofxylene. The autoclave is sealed and heated to a temperature of to 150 C.under a pressure of 30 atmospheres of nitrogen for a period of 4 hours.At the end of the4-hour period, heating is discontinued, the autoclaveis allowed to return to room temperature and the excess pressure isdischarged. The reaction product is recovered, and after flashing offthe solvent, is subjected to fractional distillation under'reducedpressure. The bottoms from the fractional distillation are recovered,extracted with xylene and recrystallized therefrom, said crystalscomprising the desired product, namely, 1,3,5- tris('1,3,4,5,6,7,7-heptachloro-5-norbornen-2- ylrnet'hyUbenzene.

EXAMPLE 111 In this example a mixture of 162 grams (1.0 mole) ofhexamethylbenzene and 194 grams (2.0 mole) of 1,2- dichloroethylenealong with 8 grams of di-t-butyl peroxide is placed in a rotatingautoclave which is thereafter sealed and pressured to 30 atmosphereswith nitrogen. Following this, the autoclave is heated to atemperatureof C. and maintained in a range of from 130-140 C. for a period of 4hours. At the end of the 4-hour period, heating is discontinued, theautoclave is allowed to return to room temperature and the excesspressure is discharged therefrom. After discharge of the pressure, theautoclave is opened and the reaction mixture is recovered, neutralizedto remove the hydrogen chloride produced during the reaction andsubjected to fractional distillation under reduced pressure. The desiredcompound comprising a mixture of bis(3-chloroallyl)-2,3,5,6-tetramethylbenzenes is recovered from thedistillation.

To a second rotating autoclave is added 1 mole proportion of the productprepared in the above paragraph along with 2 mole proportions ofhexachlorocyclopentadiene. In addition 100 cc. of toluene which acts asa solvent is added to the autoclave which is thereafter sealed,pressured with 30 atmospheres of nitrogen and heated to a temperature of125 C. The autoclave is maintained at this temperature and pressure fora period of 4 hours, at the end of which time heating is discontinued.Upon reaching room temperature, the ex cess pressure is discharged, theautoclave is opened and the reaction mixture is recovered therefrom.After flashing off the solvent and subjecting the mixture to fractionaldistillation under reduced pressure, the bottoms are recovered andrecrystallized from methanol or mesitylene. The recovered crystalscomprise the desired product, namely, 1,4-bis( 1,3 ,4,5 ,6,7,7- hep tachloro'5-norbornen-2ylmethyl)-2,3,5,6-tetramethylbenzene. I

EXAMPLE IV In a manner similar to that set forth in the above examples,1 mole proportion of meta-xylene is reacted with 2 mole proportions of1,2-dichloroethylene, said reaction being effected in a rotatingautoclave in the presence of di-t-butyl peroxide at a temperature of 130140 C. and at a pressure of 30 atmospheres for a period of4 hours. Atthe end of the 4-hour period, the autoclave is allowed to return to roomtemperature, the excess pressure is discharged and the reaction productis treated in a manner similar to that set forth in the above examples.

The desired reaction product which is prepared according to the aboveparagraph and which comprises 1,3-bis(3-chloroallyl)benzene is reactedwith l,2,3,4- tetrachlorocyclopentadiene, the reactants being present inan amount of 1 mole proportion of the chloroallylbenzene to two moleproportions of the cyclopentadiene. The condensation is effected bytreating the reactants in a rotating autoclave in the presence ofbenzene at a temperature of 125 C. for a period of 4 hours. The reactionproduct which is recovered from the autoclave after the desiredresidence time has elapsed is subjected to fractional distillation andrecrystallization of the bottoms whereby the desired product comprising1,3-bis( 1,3 ,4,5 ,6-pentachloro-5- norbornen-Z-ylmethyl)benzene isseparated and recovered.

EXAMPLE V To an alkylation flask is added 120 grams 1.0 mole) of1,3,5-trimethylbenzene (mesitylene) and 291 grams (3.0 mole) of1,2-dichloroethylene along with 5 grams of benzoyl peroxide. The mixtureis heated under reflux at a temperature of 90 C. and maintained at thistemperature for a period of 0.5 hours, the evolution of hydrogenchloride taking place during this period. The mixture is allowed to coolto room temperature and an additional 5 grams of benzoyl peroxide isadded. The mixture is again heated at 90 C. for an additional period of2 hours, cooled and 5 grams of benzoyl peroxide is again added and themixture heated to reflux for 1.5 hours more. At the end of this time,heating is discontinued, the reaction mixture is allowed to cool to roomtemperature and the reaction mixture is subjected to fractionaldistillation under reduced pressure. The desired product comprising1,3,5 -tris( 3- chloroallyl)benzene is recovered from the fractionaldistillation. Following this, 1 molecular proportion of this product istreated with 3 molecular proportions of1,2,3,4-tetrachlorocyclopentadiene in a second a1kylation flask at atemperature of 150 C. for a period of 4 hours, said reaction beingeffected in the presence of 100 grams of a solvent comprisingtetrahydronaphthalene. At the end of the 4-hour period, heating isdiscontinued and after the flask has cooled, the reaction product isrecovered and subjected to fractional distillation under reducedpressure. The bottoms from the distillation are treated with propanoland crystals recrystallized therefrom, said crystals being the desiredproduct, namely, 1,3,5-tris-( l ,3,4,5,6-pentachloro-5-norbornen-2-ylmethyl )benzene.

EXAMPLE VI In this example a novel composition of matter of the presentinvention is pre pare d by admixing 100 parts of a commercial highmolecular weight polyethylene with 15 parts of the flame retardantl,4-bis-(1,3,4,5,6,7,7- heptachloro-S-norbornen-2-ylmethyl )benzene.Following the physical admixture of the components of the finishedcomposition of matter, the composition is extruded and formed into flat,rectangular strips which contain a glass cloth in the center to preventdripping. In addition, a set of rectangular strips similar in nature areformed by extruding only the commercial high molecular weightpolyethylene. The two sets of strips are subjected to an oxygen indexcombustion test utilizing an apparatus similar to that described by C.P. Fennimore and J. F. Martin in the November, 1966 issue of ModernPlastics. The results of this test which measures the oxygen index (thelowest mole fraction of oxygen which is sufficient to maintaincombustion) will show that the strip consisting only of polyethylenewill have an oxygen index of 0.180 while the strip which comprises themixture of the polyethylene and the 1,4- bis( 1,3 ,4,5,6,7,7-heptachIoro-5-norbornen-2- ylmethyl)benzene will possess anoxygen index greatly in excess of this number.

A second series of tests are also performed in conformity with the testknown as Underwriters Laboratories Test Subject 94 or 746. In this test,a flat, rectangular specimen of material is prepared measuringapproximately 5 inches long by 0.5 inches wide. Three specimens are agedin a full-draft circulating air oven for 168 hours at a temperature ofapproximately C. Immediately after completion of the l68-hour period,the specimens are removed from the oven and cooled over calcium chloridein a dessicator for at least 4 hours at room temperature before testing.In addition, three identical unaged specimens are also tested. Inperforming the test, one of the aged specimens, with its longitudinalaxis vertical, is supported by a clamp at its upper end so that itslower end is 12 inches above a flat horizontal layer of untreatedsurgical cotton. An unlighted Bunsen burner whose barrel has an insidediameter of three-eighth inch is supported under the specimen with thelongitudinal axis of the barrel vertical and coincident with thelongitudinal axis of the specimen, the tip of the barrel beingthree-eighth inch below the specimen. With the burner so supported andnot in proximity to the specimen, the burner is ignited and adjusted toproduce a steady blue flame with an overall height of three-fourth inch.The tests are conducted in a hood which is operated to provide adequateventilation, but does not affect the flame. The burner flame is movedinto position under the specimen, kept there for 10 seccles or flamingdrops fall from the specimen and ignite the cotton.

The material of which the specimen is representative is acceptable ifflaming of the specimen ceases within 10 seconds and if the cotton isnot ignited by any particles or drops released during or after theapplication of the burner flame. If the specimen is acceptable to theseconditions, the burner flame is returned immediately to its positionunder the specimen immediately after flaming of the specimen ceases,kept there for 10 seconds and then removed. The material is acceptableif flaming of thespecimen ceases within 10 seconds, glowing ceaseswithin 10 seconds after flaming ceases and if the cotton is not ignitedby any particles or drops released during or after application of theburner flame.

If the first specimen passes the two trials set forth above, the trialsare repeated on the two remaining aged specimens and the average of thesix durations of flaming is determined. The material of which the threespecimens are representative is acceptable if the average duration doesnot exceed 5 seconds. If the three aged specimens are acceptable, theprocedure is repeated on the three remaining unaged specimens. It willbe found that the strip which contains only the polyethylene will burnand will not be selfextinguishing while the strips which contain the1,4- bis( 1,3,4,5,6,7,7-heptachloro-5-norbornen-2- ylmethyl)benzene willhave a relatively short time to self-extinguishment and either have asmall amount of dripping or melting or no burning drops of material onthe cotton.

EXAMPLE VII A novel composition of matter of the present invention isprepared by admixing 100 parts ofa commercial high molecular weightpolypropylene along with 25 parts of 1,3 ,5-tris( 1,3 ,4,5,6,7,7-heptachloro-5- norbornen-Z-ylmethyl)benzene. After physicaladmixture of the two components of the novel composition of matter, theresulting admixture is extruded into strips of material similar to thatset forth in Example VI above. Another set of strips is prepared andextruded using only the high molecular weight polypropylene. Followingthe preparation of the strips, they are subjected to an oxygen indextest similar to that which was used in Example VI above. It will befound that the oxygen index of the commercial high molecular weightpolypropylene alone is 0.180 while the oxygen index of the novelcomposition of matter of the present invention will be considerably inexcess of this figure. Likewise, when the polypropylene alone and thenovel composition of matter of the present invention comprising anadmixture of polypropylene and 1,3,5-tris(1,3,4,5,6,7,7-heptachloro-5-norbornen-2- ylmethyl)benzene is testedaccording to Underwriters Laboratories Test Subject 94, it will be foundthat the novel composition of matter will show a short time toself-extinguishment with little or no burning drops of material, whilethat of the polypropylene alone will show burning with noself-extinguishment.

EXAMPLE VIII In a manner similar to that set forth in the aboveexamples, a mixture of an acrylonitrile-butadiene-styrene formulationknown in the trade as ABS and 1,4- bis(l,3,4,5,6,7,7-heptachloro-5-norbornen-2- ylmethyl)benzene is prepared byadmixing parts of the ABS with 20 parts of the substituted benzene. Theresulting admixture after extrusion is subjected to oxygen index and ULTSubject 94 tests in a manner similar to that set forth in the aboveexamples. These compositions of matter are compared with specimens whichare prepared from only ABS. It will be found that the strips of thenovel composition of matter of the present invention will possess anoxygen index greater than that of the commercial ABS formulation alone,the latter being 0.183. In addition specimens of the mixture of ABS and1,4-bis( l,3,4,5,6,7,7-hetachloro-5- norbornen-Z-ylmethyl)benzene whentested according to the method set forth in ULT Subject 94 will be foundto be self-extinguishing as compared to the ABS form ulation which willburn and will not be selfextinguishing.

EXAMPLE IX In this example 100 parts of an epoxy resin formed by thereaction between epichlorohydrin and bisphenol-A is admixed with 15parts of 1,3-bis(1,3,4,5,6- pentachloro-S-norbornen-2-ylmethyl)benzene.After physical admixture and cooling of the resin-benzene mixture, thecured composition of matter is cut into strips. These strips aresubjected to oxygen index and ULT Subject 94 tests in comparison withstrips which were prepared from only the epoxy resin. The strips whichcomprised the novel composition of matter of the present invention willbe found to have an oxygen index greater than that which is possessed bythe epoxy resin alone and in addition will also exhibit non-burning andself-extinguishing characteristics as opposed to the epoxy resin stripwhich will burn and will not be selfextinguishing.

EXAMPLE X In like manner a novel composition of matter of the presentinvention is prepared from a polyester resulting from the reaction ofmaleic anhydride and propylene glycol which has been cross-linked withstyrene. The polyester and the flame retardant compound comprising1,3,5-tris( 1,3,4,5 ,6-pentachloro-5 -norbornen-2- ylmethyl)benzene areadmixed in a ratio of 100 parts of the polyester to 20 parts of thesubstituted benzene. The resulting composition of matter is extrudedafter milling and is cut into strips. These strips are subjected to anoxygen index test and compared to strips which have been formed only ofthe polyester. It will be found that the former strips will possess anoxygen index greatly in excess of that which is possessed by thepolyester strips alone. Other comparisons are made between the stripscomprising the novel composition of matter and the polyester aloneutilizing the ULT Subject 94 test method. The polyester strips alonewill burn and will not be self-extinguishing as compared to the stripscomprising a mixture of the polyester and 1,3,5- tris( 1 ,3,4,5,6-pentachloro-5-norbornen-2- ylmethyl)benzene; that is, these latterstrips possess a short time to self-extinguishment with little or noamount of burning material falling therefrom.

I claim as my invention:

1. A compound having the formula:

wherein X is hydrogen or chlorine or bromine, at least two Xs beingchlorine or bromine, R is hydrogen or lower alkyl, R is hydrogen oralkyl of from 1 to about 4 carbon atoms, and n is an integer of from 2to 6.

2. A compound as defined in claim 1 wherein X is chlorine.

3. A compound as defined in claim I wherein X is bromine.

4. The compound of claim 1 being 1,4- bis( 1,3 ,4,5,6,7,7-heptachloro-5-norbornen-2- ylmethyl)benzene.

5. The compound of claim 1 being 1.3.5- tris( l ,3,4,5,6,7,7-heptachloro-S-norbornen-2- ylmethyl)benzene.

6. The compound of claim 1 being 1,4-

1. A COMPOUND HAVING THE FORMULA:
 2. A compound as defined in claim 1wherein X is chlorine.
 3. A compound as defined in claim 1 wherein X isbromine.
 4. The compound of claim 1 being1,4-bis(1,3,4,5,6,7,7-heptachloro-5-norbornen-2-ylmethyl)benzene.
 5. Thecompound of claim 1 being1,3,5-tris(1,3,4,5,6,7,7-heptachloro-5-norbornen-2-ylmethyl)benzene. 6.The compound of claim 1 being1,4-bis(1,3,4,5,6,7,7-heptachloro-5-norbornen-2-ylmethyl)-2,3,5,6-tetramethylbenzene.
 7. The compound of claim 1 being1,3-bis(1,3,4,5,6-pentachloro-5-norbornen-2-ylmethyl)benzene.
 8. Thecompound of claim 1 being1,3,5-tris(1,3,4,5,6-pentachloro-5-norbornen-2-ylmethyl)benzene.